Chloroselenobenzene → HCID 49856182, compound

Temperature

-78 °C

NaHMDS (1 M solution in THF-heptanes, 1.8 mL, 1.8 mmol) was slowly added to a solution of 11 (320 mg, 0.75 mmol) in dry THF (20 mL) at −78° C. The reaction mixture was stirred at −78° C. for 1 h, and then a solution of phenylselenyl chloride (216 g, 1.13 mmol) in dry THF (5 mL) was added dropwise and the mixture was stirred at −78° C. for 2 h. The reaction mixture was allowed to warm to room temperature and stirred at this temperature for 3 h. The reaction mixture was quenched by slow addition of 1N HCl (5 mL) at 0° C., diluted with water (50 mL) and extracted with chloroform (4×50 mL). The combined extracts were washed with water and brine, dried with sodium sulfate, and evaporated under reduced pressure. The residue was dissolved in THF (10 mL). Acetic acid (1 mL) and hydrogen peroxide (30%, 5 mL) were added sequentially at 0° C. The reaction mixture was warmed to room temperature and stirred for 6 h. Saturated aqueous sodium bicarbonate (5 mL) was added to the mixture at 0° C. Chloroform (3×10 mL) was used to extract the product. The combined extracts were washed with water and brine, dried with sodium sulfate, and evaporated to afford the product (198 mg, 62%): mp 165-170° C. IR (film) 1730, 1718, 1638 cm−1; 1H NMR (500 MHz, CDCl3) δ 8.05 (d, J=6.2 Hz, 1 H), 7.86 (s, 1 H), 7.49 (t, J=7.9 Hz, 1 H), 7.22-7.16 (m, 2 H), 7.16-7.11 (m, 1 H), 6.53 (s, 1 H), 4.04 (s, 3 H), 3.99 (s, 3 H), 3.72 (s, 3 H), 3.45 (s, 3 H), 3.24 (s, 3 H); 13C NMR (126 MHz, CDCl3) δ 167.39, 162.03, 154.22, 154.07, 150.14, 139.65, 136.41, 130.97, 129.29, 128.59, 124.49, 119.35, 112.69, 108.14, 104.80, 56.52, 56.37, 52.75, 52.26, 33.18; ESIMS m/z (rel intensity) 449 (18), 427 (MH+, 100), 395 (78); ESIHRMS m/z MH+ calcd. for C22H22N2O7, 427,1505; found, 427.1507.

1. stirringthe mixture was stirred at −78° C. for 2 h
2. temperatureto warm to room temperature
3. stirringstirred at this temperature for 3 h
4. customThe reaction mixture was quenched by slow addition of 1N HCl (5 mL) at 0° C.
5. additiondiluted with water (50 mL)
6. extractionextracted with chloroform (4×50 mL)
7. washThe combined extracts were washed with water and brine
8. dry with materialdried with sodium sulfate
9. customevaporated under reduced pressure
10. dissolutionThe residue was dissolved in THF (10 mL)
11. additionAcetic acid (1 mL) and hydrogen peroxide (30%, 5 mL) were added sequentially at 0° C
12. temperatureThe reaction mixture was warmed to room temperature
13. stirringstirred for 6 h
14. additionSaturated aqueous sodium bicarbonate (5 mL) was added to the mixture at 0° C
15. extractionto extract the product
16. washThe combined extracts were washed with water and brine
17. dry with materialdried with sodium sulfate
18. customevaporated

ORD record

ord-07dc8c39e1d246a2ae4e1ef6249e7250

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09073920B2